Indian Journal of Chemical Technology
Vol. 15, September 2008, pp. 511-514
Distribution of Cr (III) and Cr (VI) in chrome
tanned leather
Bahri Başaran*, Mete Ulaş, Behzat Oral Bitlisli & Ahmet
Aslan
Leather Engineering Department, Faculty of Engineering,
Ege University, TR-35100, Izmir,Turkey
Email: bahri.basaran@ege.edu.tr
Received 7 March 2007; revised 28 May 2008
Basic chromium sulphate is the most versatile and common
tanning agent in the leather industry. Under certain circumstances,
the oxidation of the trivalent chromium salts into the hexavalent
compounds, which are used in leather manufacture, is a crucial
issue. In this study, different proportions of basic chromium
sulphate were used in tanning and re-tanning processes according
to a commonly used recipe, and levels of chromium oxide and
hexavalent chromium were studied stratigraphically in the cross-
section of the leather. It was observed that the levels of chromium
oxide and hexavalent chromium in the skins increased in relation
to the proportions of basic chromium sulphate used in the process,
and that the amounts added in the tanning process had a greater
effect on the levels of hexavalent chromium formed in the layers
of the skins than did the amounts added in re-tanning.
Keywords: Skin, Tanning, Chromium oxide, Chromium (VI),
Tanned leather
The leather manufacturing industry processes raw
skins and hides for various purposes. Raw skins are
transformed into stable finished products by a series
of chemical and mechanical processes1,2. Among
these processes, tanning is very importance. In the
leather industry, tanning means the conversion of raw
skin into finished leather through various technical
processes3. Unless the tanning process is carried out,
the raw skin protein, which is made of collagen, will
putrefy and progressively deteriorate4. The collagen
proteins will deform when heated, and in water they
will turn into gelatine5. Thus, tanning is an essential
process for the conversion of the collagens in natural
skin and hides into a stable form, giving the material
individual durability by allowing the penetration of
various tanning agents with different characteristics
into the structure through mechanical action in floats
and by reaction with reactive groups of collagens1,3,5.
Tanning agents are not only used in the tanning
process, but they can also be used in another stage,
which is called re-tanning/retannage, to further
achieve the final features5.
Now-a-days the use of chromium has accelerated
in the leather industry as it enables faster and cheaper
production of highly resistant and durable leathers6,7.
Today, more than 80% of finished goods are tanned
using basic chromium salts8,9. However, high pH
value, temperature, UV lights, unsuitable storage
conditions and the effect of using lubricants with
double bonds in the molecule during production,
possibly turn up the oxidation of the trivalent
chromium into the hexavalent form10-16. For this
reason, a limit of 3-50 ppm has been imposed by
various countries on the level of Cr (VI) in leather13.
Since 1994, when the formation of chromate
complexes in leather goods was identified, strong
pressure has been put on the global leather industry by
both consumers’ rights associations and
environmental protection organisations17 to reduce its
content in the leather. This has had a great effect on
leather exporting countries, and many researches have
been devoted to this subject. Studies have been
undertaken for identifying the factors responsible for
oxidation, reducing or completely eliminating the use
of chromium in tanning, the determination of
hexavalent chromium in the leather, and problems
related to analysis methods18-21. It is likely that
chromium tanning will be in use for years to come
because of the characteristics it imparts to final
products and its ease of application. This study
examined the stratigraphic distribution of 3- and 6-
valent chromium compounds in the leather, and
determined the relation between the amount of
chromium used in tanning and the formation of
hexavalent chromium in the leather.
Experimental Procedure
Materials
Eighteen standard quality commercially pickled
sheep skins with a thickness of 1.0-1.2 mm and a pH
value of 2.0 were used. Because of their bilateral
features, these skins were cut into two equal parts
down their backbones22. The experiments were
carried out on 36 sides obtained in this way.
Tanning of skins
The sides were divided into 3 groups and these
groups were tanned with 33% basic chromium
sulphate in proportions of 4, 6 and 8%. Subsequently,
512 INDIAN J. CHEM. TECHNOL., SEPTEMBER 2008

the skin groups were divided into 3 sub-groups and

chromium re-tanning was carried out by adding 33%
basic chromium sulphate in proportions of 2, 4 and
6%. The process recipes are given in Tables 1 and 2.
After the tanning and re-tanning, the skins were
stored for 6 months and then divided into three layers
in a splitting machine to determine the distribution of
3- and 6-valent chromium compounds.
Analyses
The trivalent chromium content in the leathers
ripped horizontally into layers by the splitting process
was analyzed in each split layer according to IUC/823,
and hexavalent chromium was determined according
to DIN 53314 (IUC 18)24,25. The calibration curve of
the standard solutions prepared for the determination
of chromium according to the DIN 53314 method is
Fig. 1Calibration curve of standardized solutions
given in Fig. 1.

Table 1Tanning recipe

Process Additives Temp. (oC) Prop.(%) Time (min) Remarks

Depickling Water 25 200 20 7 oBé Brine solution
Acid bating agent 1 30
Sodium formate 0.5 30
Sodium bicarbonate 1 45 pH: 5.5 / Keep overnight
Fleshing
Degreasing Alkyl polyglycol ether 3 120 Drain
Washing Water 35 200 20 Drain
Washing Water 35 200 20 Drain
Pickling Water 150 20 6° Bé
Formic acid 4.0 40
Sulphuric acid 0.5 60 pH : 2.9
Tanning Basic chromium sulphate X 240 X= 4, 6 and 8%
Sodium formate 1 40
Sodium bicarbonate 0.8 60
Sodium bicarbonate 1.0 20 pH: 3.8, Drain
Washing Water 25 200 30 Drain, horse up (3 days)
Table 2Re-tanning recipe
Washing Water 35 300
Formic acid 0.3
Alkyl polyglycol ether 0.3 30 Drain
Washing Water 35 300 10 Drain
Re-tanning Water 32 150
Aliphatic dicarboxylic acid salts 0.5 30
Basic chromium sulphate X 240 X= 2, 4 and 6 %
Phenol sulphonic acid condensate 2 30
Sodium formate 0.5 15
Sodium bicarbonate 0.5 15 pH: 4.2
Naphtalene sulphonic acid condensate 2 30
Formic acid 0.5 30 Drain
Washing Water 25 200 20 Drain
 NOTES 513

Results and Discussion
Distribution of the proportions of chromium oxide
(Cr2O3) and Cr (VI) in the lower, middle and upper
parts of the split leathers are given in Table 3. From
the results it can be seen that the maximum chromium
oxide amounts were found in the lower split part of
the leathers, and the amounts decreased towards the
upper split parts. When the effect of basic chromium
sulphate proportion was observed, it was found that
the maximum chromium oxide concentration was
found when 6% basic chromium sulphate was used,
and the minimum chromium oxide contents resulted
from the addition of 2% basic chromium sulphate.
These results indicated that when the basic chromium
sulphate concentration added to the skins is increased,
the chromium oxide content of leather also increases.
In terms of providing the performance
characteristics satisfactorily, it is recommended that
chrome tanned leathers should include a minimum of
2.5% chromium oxide26. Unless an appropriate

Table 3Distribution of Cr2O3 and Cr (VI) in the sections of leather layers

Leathe Chrome added in Chrome added in Cr2O3 Cr(VI)

r tanning (%) re-tanning (%) determined determined
Layer (%) (ppm)
Mea Averag Mea Averag
n e SD n e SD
Lower 4 2 3.57 7.14
4 4 3.74 0.17 7.73 0.62
4 6 3.90 8.39
Lower 6 2 3.85 7.79
6 4 3.94 0.14 8.58 0.83
6 6 4.12 9.45
Lower 8 2 10.5
8 3.94 7
8 4 11.2
0.16 0.52
4.18 4
6 11.5
4.25 9
Middle 4 2 3.29 6.76
4 4 3.43 0.11 6.74 0.77
4 6 3.50 8.09
Middle 6 2 3.50 8.49
6 4 3.54 6.20 8.82 0.50
6 6 3.62 9.48
Middle 8 2 11.4
8 3.88 5
8 4 11.0
2.67 1.44
3.93 3
6 11.7
3.93 0
Upper 4 2 3.23 6.38
4 4 3.29 7.95 6.71 0.17
4 6 3.38 6.63
Upper 6 2 3.32 7.14
6 4 3.42 6.53 7.80 0.34
6 6 3.45 7.59
Upper 8 2 3.50 7.85
8 4 3.57 5.59 8.36 0.37
8 6 3.61 8.57
514 INDIAN J. CHEM. TECHNOL., SEPTEMBER 2008
tanning practice is applied, the durability of the
finished goods might be unsatisfactory and the
hydrothermal stability can be lower than acceptable
quality levels. In addition, other undesirable features
such as the lacks in appearance and handling
problems occur27. In this study, the chromium oxide
content of the tanned goods was found to be more
than the suggested lower limit value.
The maximum hexavalent chromium contents were
found in the lower split part of the leathers, whereas
the least contents were found in the upper split parts.
It was observed that as the amounts of added basic
chromium sulphate increased in the tanning process
the Cr (VI) contents in the leather also increased. The
highest hexavalent chromium levels were found in
leathers tanned with 8% basic chromium sulphate,
and the lowest hexavalent chromium levels were
found in leathers tanned with 4% basic chromium
sulphate. It was observed that when the basic
chromium sulphate amounts used in re-tanning
process were increased from 2 to 6%, the hexavalent
chromium contents also increased.
As previously indicated in relevant studies,
oxidation to hexavalent form is accelerated by high
pH values in neutralisation, chemical additives such
as ammonia, sodium bicarbonate and free unsaturated
fatty acids, exposure of leather to high temperatures
(80ºC) and UV light during processes and thereafter.
In a study28 it was observed that more the trivalent
chromium used and higher ironing temperature
applied, the higher hexavalent chromium level in both
fiber and suede side of double-faces were observed.
It was found that the basic chromium sulphate
proportions added in tanning had been more effective
both on chromium oxide contents and hexavalent
chromium formation determined in the each split parts
of the leathers than did the basic chromium sulphate
proportions added in re-tannage process. It was found
that the leathers examined in the study conformed to
the EU commission’s decision of 18 March 2002 that
the hexavalent chromium concentration must not be
over 10 ppm in finished leathers29.
Conclusion
This study reveals that the stratigraphic distribution
of chromium oxide contents and hexavalent
chromium levels are related to the proportion of
chromium sulphate added to the skin in tanning and
re-tanning processes. According to the results, the use
of 4% basic chromium sulphate is appropriate for
both tanning and re-tanning, taking into consideration
both the desired qualities of the leather and the
formation of hexavalent chromium in the leather.
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